Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes

ABSTRACT

This disclosure provides for routes of synthesis of acrylic acid and other α,β-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the α,β-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/377,563, filed Dec. 13, 2016, which claims the benefit of U.S.Provisional Patent Application No. 62/267,601, filed Dec. 15, 2015, eachof which is incorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This disclosure relates to routes of synthesis of acrylic acid and otherα,β-unsaturated carboxylic acids, including catalytic methods.

BACKGROUND

The majority of industrially synthesized chemical compounds are preparedfrom a limited set of precursors, whose ultimate sources are primarilyfossil fuels. As these reserves diminish, it would be beneficial to usea renewable resource, such as carbon dioxide, which is a non-toxic,abundant, and economical C₁ synthetic unit. The coupling of carbondioxide with other unsaturated molecules holds tremendous promise forthe direct preparation of molecules currently prepared by traditionalmethods not involving CO₂.

One could envision the direct preparation of acrylates and carboxylicacids through this method, when carbon dioxide is coupled with olefins.Currently, acrylic acid is produced by a two-stage oxidation ofpropylene. The production of acrylic acid directly from carbon dioxideand ethylene would represent a significant improvement due to thegreater availability of ethylene and carbon dioxide versus propylene,the use of a renewable material (CO₂) in the synthesis, and thereplacement of the two-step oxygenation process currently beingpracticed.

Therefore, what is needed are improved methods for preparing acrylicacid and other α,β-unsaturated carboxylic acids, including catalyticmethods.

SUMMARY OF THE INVENTION

This summary is provided to introduce various concepts in a simplifiedform that are further described below in the detailed description. Thissummary is not intended to identify required or essential features ofthe claimed subject matter nor is the summary intended to limit thescope of the claimed subject matter.

In an aspect, this disclosure provides processes, including catalyticprocesses, for producing α,β-unsaturated carboxylic acids or saltsthereof utilizing a soluble or an insoluble anionic polyelectrolytesystem. When the anionic polyelectrolyte system is insoluble or thereaction system is otherwise heterogeneous, these processes represent animprovement over homogeneous processes that result in poor yields andinvolve challenging separation/isolation procedures. Therefore,conventional methods generally make isolation of the desiredα,β-unsaturated carboxylic acid (e.g., acrylic acid) difficult. Incontrast, the processes disclosed herein utilize an anionicpolyelectrolyte having associated metal cations that generally providesa heterogeneous reaction mixture. When combined with a catalyst such asa nickel catalyst, ethylene and carbon dioxide can be coupled to form ametalalactone, and the anionic polyelectrolyte can subsequentlydestabilize the metalalactone which eliminates a metal acrylate. Bydeveloping the disclosed heterogeneous system, there is now provided adistinct advantage in ease of separation of the desired product from thecatalytic system. Moreover, the anionic polyelectrolytes can result insurprisingly high yields of the desired α,β-unsaturated carboxylic acid,such as acrylic acid.

According to an aspect, one such process for producing anα,β-unsaturated carboxylic acid, or a salt thereof, can comprise:

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to        induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or a salt thereof.

In a further aspect, there is provided another such process for theformation of an α,β-unsaturated carboxylic acid, or a salt thereof, andthis process can comprise:

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture comprising an adduct            of the metalalactone and the anionic polyelectrolyte and its            associated metal cations; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.

According to additional aspects of this disclosure, there is provided aprocess for producing an α,β-unsaturated carboxylic acid or a saltthereof, in which this process can comprise:

-   -   (1) contacting in any order        -   (a) a transition metal precursor compound comprising at            least one first ligand;        -   (b) optionally, at least one second ligand;        -   (c) an olefin;        -   (d) carbon dioxide (CO₂);        -   (e) a diluent; and        -   (f) an insoluble anionic polyelectrolyte having associated            metal cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.

This summary and the following detailed description provide examples andare explanatory only of the invention. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Additional features or variations thereof can beprovided in addition to those set forth herein, such as for example,various feature combinations and sub-combinations of these described inthe detailed description.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE illustrates an embodiment or aspect of this disclosure,showing the use of an anionic polyelectrolyte stationary phase in acolumn configuration, in which formation of the acrylate couplingreaction of ethylene and CO₂ to form a metalalactone such as anickelalactone in a mobile phase can be effected, and the resultingnickelalactone destabilized by the polyelectrolyte stationary phase toform an acrylate product.

DETAILED DESCRIPTION OF THE INVENTION Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “ananionic polyelectrolyte,” “a diluent,” “a catalyst,” and the like, ismeant to encompass one, or mixtures or combinations of more than one,anionic polyelectrolyte, diluent, catalyst, and the like, unlessotherwise specified.

The term “hydrocarbon” refers to a compound containing only carbon andhydrogen. Other identifiers can be utilized to indicate the presence ofparticular groups in the hydrocarbon, for instance, a halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon.

As used herein, the term “α,β-unsaturated carboxylic acid” and itsderivatives refer to a carboxylic acid having a carbon atom of acarbon-carbon double bond attached to the carbonyl carbon atom (thecarbon atom bearing the double bonded oxygen atom). Optionally, theα,β-unsaturated carboxylic acid can contain other functional groups,heteroatoms, or combinations thereof.

The term “polyelectrolyte” is used herein to mean a polymeric(macromolecular) substance which comprises a multiply-charged polyion,together with an equivalent amount of counter ions. Therefore, an“anionic polyelectrolyte” refers to a polyelectrolyte that comprises amultiply-charged polyanion, together with an equivalent amount ofcations. The charge on the polyion typically resides on heteroatoms suchas oxygen, nitrogen or sulfur, or on groups such as sulfonate. Thestructural part of the polyelectrolyte that bears the charged moietiescan be pendant groups off a polymer backbone or can be part of thepolymeric backbone itself. The term “polyelectrolyte” is used to referto both soluble species and insoluble species, such as some of thepoly(vinylphenol)-based materials and the phenol-formaldehyde basedmaterials described herein. The multiply-charged polyanion may also bereferred to as a base, and the associated metal ion as simply a counterion, metal ion, or Lewis acid as appropriate.

Although the terms “polyphenol” and “polyaromatic” are used herein todescribe anionic polyelectrolytes in which a phenoxide moiety carriesthe negative charge in the polyelectrolyte, and although these terms maybe used interchangeably as the context allows, these terms are generallyused herein to describe specific types of anionic polyelectrolytepolymers that are somewhat different, as set out here.

[1] The terms “polyphenol” and “polyphenoxide” are generally used hereinto describe a specific type of anionic polyelectrolyte polymer, forexample, the polymeric materials such as poly(4-vinylphenol) andmetallated poly(4-vinylphenoxide) that typically include a pendantphenol, phenoxide, or substituted analogs thereof that are bonded to apolymeric backbone. Therefore, the oxygen of the phenoxide group bearsthe negative charge.

[2] The term “polyaromatic” is also generally used herein to describe aspecific type of anionic polyelectrolyte resin or polymer, for example,the phenol-formadehyde crosslinked resins and their analogs, in whichthe phenol aromatic group and methylene moieties are part of an extendedcrosslinked network. Therefore, aromatic groups in the “polyaromatic”structure are hydroxylated, hydroxymetallated, or otherwisefunctionalized with a group that carries the negative charge in theanionic polyelectrolyte (e.g. thiolate, alkyl amide). Crosslinkednetworks that are prepared using various phenol or polyhydroxyareneco-monomers are also included in this definition. The term “phenolicresin” may be used to describe these materials as well.

A “polyhydroxyarene” is used herein to a phenol-type monomer thatincludes more than one hydroxyl group. Resorcinol (also termed,benzenediol or m-dihydroxybenzene) is a typical polyhydroxyarene.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all conformational isomers,regioisomers, stereoisomers, and mixtures thereof that can arise from aparticular set of substituents, unless otherwise specified. The name orstructure also encompasses all enantiomers, diastereomers, and otheroptical isomers (if there are any) whether in enantiomeric or racemicforms, as well as mixtures of stereoisomers, as would be recognized by askilled artisan, unless otherwise specified. For example, a generalreference to pentane includes n-pentane, 2-methyl-butane, and2,2-dimethylpropane; and a general reference to a butyl group includes an-butyl group, a sec-butyl group, an iso-butyl group, and a t-butylgroup.

Various numerical ranges are disclosed herein. When Applicants discloseor claim a range of any type, Applicants' intent is to disclose or claimindividually each possible number that such a range could reasonablyencompass, including end points of the range as well as any sub-rangesand combinations of sub-ranges encompassed therein, unless otherwisespecified. Moreover, all numerical end points of ranges disclosed hereinare approximate. As a representative example, Applicants disclose, in anaspect of the invention, that one or more steps in the processesdisclosed herein can be conducted at a temperature in a range from 10°C. to 75° C. This range should be interpreted as encompassingtemperatures in a range from “about” 10° C. to “about” 75° C.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants can be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants canbe unaware of at the time of the filing of the application.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe the compound or group wherein any non-hydrogen moiety formallyreplaces hydrogen in that group or compound, and is intended to benon-limiting. A compound or group can also be referred to herein as“unsubstituted” or by equivalent terms such as “non-substituted,” whichrefers to the original group or compound. “Substituted” is intended tobe non-limiting and include inorganic substituents or organicsubstituents as specified and as understood by one of ordinary skill inthe art.

The terms “contact product,” “contacting,” and the like, are used hereinto describe compositions and methods wherein the components arecontacted together in any order, in any manner, and for any length oftime, unless specified otherwise. For example, the components can becontacted by blending or mixing. Further, unless otherwise specified,the contacting of any component can occur in the presence or absence ofany other component of the compositions and methods described herein.Combining additional materials or components can be done by any suitablemethod. Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can, and often does, includereaction products, it is not required for the respective components toreact with one another. Similarly, “contacting” two or more componentscan result in a reaction product or a reaction mixture. Consequently,depending upon the circumstances, a “contact product” can be a mixture,a reaction mixture, or a reaction product.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

The present disclosure is directed generally to methods for formingα,β-unsaturated carboxylic acids, or salts thereof. An illustrativeexample of a suitable α,β-unsaturated carboxylic acid is acrylic acid.

According to one aspect, this disclosure provides for the formation ofan α,β-unsaturated carboxylic acids and salts thereof frommetalalactones and anionic polyelectrolytes. One example of theα,β-unsaturated carboxylic acid salt formation from exemplarymetalalactones and anionic polyelectrolytes is illustrated in Scheme 1,which provides for a nickel catalytic coupling reaction between anolefin and CO₂ and formation of an acrylate. As explained herein, Scheme1 is not limiting but is exemplary, and each reactant, catalyst,polymer, and product are provided for illustrative purposes.

In Scheme 1, a transition metal catalyst as disclosed herein isillustrated generally by a nickel(0) catalyst at compound 1, and theolefin disclosed herein, generally an α-olefin, is illustrated generallyby ethylene. In the presence of the catalyst 1, the olefin couples withCO₂ to form the metalalactone 2. Metalalactone 2 is destabilized by itsinteraction with an anionic polyelectrolyte, an example of which isshown in Scheme 1 as a metal poly(4-vinylphenoxide) 3. While notintending to be bound by theory, metal poly(4-vinylphenoxide) 3 isthought to interact with metalalactone 2 in some way, for example toform an adduct of some type, such as one illustrated as adduct 4.Reaction with the combined metal poly(4-vinylphenoxide) 3 andmetalalactone 2 (or adduct of some type, represented generally as 4)with a base 5 both eliminates or releases the metal acrylate 6 fromadduct 4 and regenerates catalyst compound 1 and byproduct neutralpolymer (here, poly(4-vinylphenol), which is regenerated to the anionicpolyelectrolyte reactant, for example metal poly(4-vinylphenoxide) 3,upon its reaction with the base 5. In other words, elimination of themetal acrylate from 4 occurs to regenerate catalyst compound 1 andbyproduct neutral polymer (here, poly(4-vinylphenol)), which isregenerated to the anionic polyelectrolyte reactant 3 upon its reactionwith a base 5. In the presence of additional ethylene and CO₂, catalyst1 is converted to metalalactone 2.

One exemplary base illustrated in Scheme 1 is a hydroxide base, but acarbonate base, similar inorganic bases, and a wide range of other basescan be used, particularly metal-containing bases. Metal containing basescan include any basic inorganic metal compound or mixture of compoundsthat contain metal cations or cation sources, for example, alkali andalkaline earth metal compounds such as oxides, hydroxides, alkoxides,aryloxides, amides, alkyl amides, arylamides, and carbonates likecalcium hydroxide. In an aspect, the reaction of Scheme 1 can beconducted using certain bases as disclosed, but if desired, otherorganic bases such as some alkoxide, aryloxide, amide, alkyl amide,arylamide bases, or the like can be excluded. Typically, the inorganicbases such as alkali metal hydroxides have been found to work well.

Generally, the anionic polyelectrolyte and associated cations used inthe processes disclosed herein can comprise (or consist essentially of,or consist of) an insoluble anionic polyelectrolyte, a soluble anionicpolyelectrolyte, or a combination thereof. That is, the anionicpolyelectrolyte material can be soluble, insoluble, or only partially orslightly soluble in the diluent or reaction mixture. It is furthercontemplated that mixtures or combinations of two or more anionicpolyelectrolytes can be employed in certain aspects of the disclosure.Therefore, the “anionic polyelectrolyte” is a polymeric material whichcomprises a multiply-charged polyanion, together with an equivalentamount of counter cations, and is used generally to refer to bothsoluble materials and insoluble materials.

In an aspect, the anionic polyelectrolyte (and associated cations) canbe used in the absence of an alkoxide or aryloxide base. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, and/orsubstituted analogs thereof. That is, additional bases with theirassociated counter ions are not required to effect the processesdisclosed herein.

According to an aspect, the anionic polyelectrolyte and associatedcations used in the processes can be used in the absence of a solidsupport. That is the anionic polyelectrolyte can be used in its naturalpolymeric form without being bonded to or supported on any insolublesupport, such as an inorganic oxide or mixed oxide material.

In an aspect, the term anionic polyelectrolyte is used to refer to andinclude such polyelectrolytes that comprise alkoxide, aryloxide,acrylate, (meth)acrylate, sulfonate, alkyl thiolate, aryl thiolate,alkyl amide, or aryl amine groups, along with associated metal cations,such as any alkali metal cation, alkaline earth cation, or metal cationshaving varying Lewis acidities. While aspects of this disclosure areexemplified with anionic polyelectrolytes having aryloxide (or“phenoxide”) anionic groups, these are to be considered exemplary of anyof the anionic polyelectrolytes provided herein. Therefore, terms suchas poly(vinyl aryloxide), poly(vinyl phenoxide), poly(hydroxystyrene),and the like are generally used interchangeably unless the contextprovides otherwise.

Accordingly, the term anionic polyelectrolyte is used generally toinclude such anionic polyelectrolytes as a poly(vinyl aryloxide), apoly(vinyl alkoxide), a poly(acrylate), a poly((meth)acrylate)), apoly(styrene sulfonate), a phenol-formaldehyde resin, apolyhydroxyarene-formaldehyde resin (such as a resorcinol-formaldehyderesin), a polyhydroxyarene- and fluorophenol-formaldehyde resin (such asa resorcinol- and 2-fluorophenol-formaldehyde resin), a poly(vinylarylamide), a poly(vinyl alkylamide), or combinations thereof, alongwith associated metal cations. Polymers that generally fall under thephenol-formadehyde type of crosslinked resins may be referred to aspolyaromatic resins. Co-polymers of these specific types of anionicpolyelectrolytes are also included in this disclosure. Thepolyelectrolyte core structure can be substituted on the polymerbackbone or the pendant groups that also contain the typical oxygen,nitrogen, or sulfur heteroatoms, and such substituted variations areincluded in this disclosure and use of the term anionic polyelectrolyte.For example, any of the anionic polyelectrolytes can be substituted withelectron-withdrawing groups or electron-donating groups or evencombinations thereof.

Anionic polyelectrolytes such as those used herein include associatedcations, particularly associated metal cations, including Lewis acidicmetal cations and cations with low Lewis acidity. According to anaspect, the associated metal cations can be an alkali metal, an alkalineearth metal, or any combination thereof. Typical associated metalcations can be, can comprise, or can be selected from lithium, sodium,potassium, magnesium, calcium, strontium, barium, aluminum, or zinc, andthe like. Generally, sodium or potassium associated metal cations havebeen found to work well. Therefore, cations with a range of Lewisacidities in the particular solvent can be useful according to thisdisclosure.

One aspect of the disclosed process provides for using an anionicpolyelectrolyte that comprises, consists essentially of, or consists ofsodium(polyvinylphenoxide), including sodium(poly-4-vinylphenoxide).Other salts, such as the potassium salt, of the poly-4-vinylphenoxideare also useful.

In a further aspect, useful anionic polyelectrolytes can includephenol-formaldehyde resins, which are cross-linked materials derivedfrom the condensation reaction of phenol with formaldehyde, that aretreated with a base or a metal cation source. Advantages of usingtreated phenol-formaldehyde resins include their insolubility, whichallows the use of a range of solvents with these materials, and theirrelatively high phenol concentration that can be functionalized using ametal base such as an alkali metal hydroxide. An early version of thethermosetting phenol formaldehyde resins formed from the condensationreaction of phenol with formaldehyde is Bakelite™, and variousphenol-formaldehyde resins used herein may be referred to generically as“bakelite” resins. In the context of this disclosure, the use of termssuch as bakelite or general terms such as phenol-formaldehyde resinscontemplates that these materials will be treated with ametal-containing base or a metal cation source such as sodium hydroxideprior to their use in the processes disclosed.

In addition, other useful anionic polyelectrolytes include substitutedphenol-formaldehyde resins that are also generally crosslinked intoinsoluble resins. These resins can be formed from the condensationreaction of one or more of phenol, a polyhydroxyarene such as resorcinol(also, benzenediol or m-dihydroxybenzene), and/or their substitutedanalogs with formaldehyde. Therefore, these materials include resinsmade with more than one phenol as co-monomer. Treatment with bases suchas NaOH or KOH also provides a ready method of functionalizing thepolyaromatic polymers for the reactivity described herein.

In one example, a resin can be prepared using the monomer combination ofresorcinol (m-dihydroxybenzene) and fluorophenol monomers withformaldehyde, and sodium-treated to generate the anionicpolyelectrolyte. While not intending to be theory bound, themeta-dihydroxybenzene is believed to add additional ion chelationfunctionality to the resin. Subsequent base (e.g. sodium hydroxide)treatment can be used to generate the anionic polyelectrolyte.

Finally, this aspect is not intended to be limiting. Therefore, othersuitable anionic polyelectrolytes that can be used include a number ofanionic polyelectrolytes which include carboxylic acid/carboxylategroups. Examples include but are not limited to polyacrylic acid,polymethacrylic acid, poly(D,L-glutamic) acid, polyuronic acid (alginic,galacturonic, glucuronic, and the like), glycosaminoglycans (hyaluronicacid dermatan sulphate, chondroitin sulphate, heparin, heparan sulphate,and keratan sulphate), poly(D,L-aspartic acid), poly(styrene sulfonate),poly(phosphate), polynucleic acids, and so forth.

In those aspects and embodiments in which polymer support variations areused and/or in which the polyelectrolyte itself is a solid that isinsoluble in the diluent of the reaction, such solid statepolyelectrolyte embodiments can have any suitable surface area, porevolume, and particle size, as would be recognized by those of skill inthe art. For instance, the solid polyelectrolyte can have a pore volumein a range from 0.1 to 2.5 mL/g, or alternatively, from 0.5 to 2.5 mL/g.In a further aspect, the solid polyelectrolyte can have a pore volumefrom 1 to 2.5 mL/g. Alternatively the pore volume can be from 0.1 to 1.0mL/g. Additionally, or alternatively, the solid polyelectrolyte can havea BET surface area in a range from 10 to 750 m²/g; alternatively, from100 to 750 m²/g; or alternatively, from 100 to 500 m²/g or alternativelyfrom 30 to 200 m²/g. In a further aspect, the solid polyelectrolyte canhave a surface area of from 100 to 400 m²/g, from 200 to 450 m²/g, orfrom 150 to 350 m²/g. The average particle size of the solidpolyelectrolyte can vary greatly depending upon the process specifics,however, average particle sizes in the range of from 5 to 500 μm, from10 to 250 μm, or from 25 to 200 μm, are often employed. Alternatively ⅛inch (3.2 mm) to ¼ inch (6.4 mm) pellets or beads can also be used.

The present disclosure also provides for various modifications of thepolymeric anionic stationary phase (anionic polyelectrolytes), forexample, in a column or other suitable solid state configuration.Further various modifications of the polymeric anionic stationary phase(anionic polyelectrolytes), for example, in a column or other suitablesolid state configuration are useful in the processes disclosed herein.For example, acid-base reactions that generate the anionicpolyelectrolyte from the neutral polymer can be effected using a widerange of metal bases, including alkali and alkaline hydroxides,alkoxides, aryloxides, amides, alkyl or aryl amides, and the like, suchthat an assortment of electrophiles can be used in nickelalactonedestabilization as demonstrated herein for the polyvinylphenols.

Polymer modifications can also include using variants of thepoly(vinylphenol), that can be prepared by polymerization of protectedhydroxyl-substituted styrenes (such as acetoxystyrene) having a varietyof organic and inorganic substituents, such as alkyls, halogens, andheteroatom substituents, typically followed by hydrolysis. Suchadjustments can provide flexibility for tailoring the reaction accordingto the specific olefin to be coupled with CO₂, the reaction rate, thecatalytic turnover, as well as additional reaction parameters andcombinations of reaction parameters.

In a further aspect, polymer modifications can also include usingco-polymers based on, for example, the co-polymerization of a protectedhydroxyl-substituted styrene with other monomers (e.g., styrenes and/or(meth)acrylates) to produce libraries of polymeric electrophiles. Such alibrary can be utilized to test and match the specific anionicpolyelectrolyte with the specific olefin, to improve or optimizereaction rate, catalytic turnover, reaction selectivity, and the like.Further polymer support variations can also be used, for example,polymers can be supported onto beads or other surfaces. Alternatively,one class of polymer support variation that is possible for use withthis technology is the cast polymer that can function as an ion exchangemembrane. Alternatively, the anionic polyelectrolyte can be unsupportedand used in the absence of any support.

The disclosed processes can further include the step of reacting adduct4 of the metalalactone 2 and anionic polyelectrolyte 3 with a base 5,also termed a regenerative base. The regenerative base 5 can comprise ametal ion or a metal ion source. In the example of Scheme 1, the anionicpolyelectrolyte can be a metal poly(4-vinylphenoxide), which is formedupon the reaction of the neutral polymer, for examplepoly(4-vinylphenol), with a base 5 such as a metal-containing base. Forexample, the metal in a metal-containing base can be, but is not limitedto, a metal of Groups 1, 2, 12 or 13, such as lithium, sodium,potassium, rubidium, cesium, magnesium, calcium, zinc, aluminum orgallium. As illustrated in Scheme 1, the reaction of a base 5 with thecombination of the anionic polyelectrolyte 3 and metalalactone 2 (oradduct of some type, represented generally as 4) with a metal-containingbase 5 both eliminates or releases the metal acrylate 6 from 4 andregenerates catalyst compound 1 and byproduct neutral polymer (e.g.poly(4-vinylphenol) in Scheme 1), which is regenerated to the anionicpolyelectrolyte reactant upon its reaction with a regenerative base 5.Various bases 5 can be used according to this disclosure.

The step of regenerating the anionic polyelectrolyte can be effected bycontacting the anionic polyelectrolyte with a regenerative base 5comprising a metal cation following the formation of the α,β-unsaturatedcarboxylic acid or a salt thereof. A wide range of bases 5 can be usedfor this regeneration step. For example, the regenerative base 5 can beor can comprise metal-containing bases which can include any reactiveinorganic basic metal compound or mixture of compounds that containmetal cations or cation sources, for example, alkali and alkaline earthmetal compounds such as oxides, hydroxides, alkoxides, aryloxides,amides, alkyl amides, arylamides, and carbonates. Suitable bases includeor comprise, for example, carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, Ca(OH)₂, NaOH, KOH), alkoxides (e.g.,Al(O^(i)Pr)₃, Na(O^(t)Bu), Mg(OEt)₂), aryloxides (e.g. Na(OC₆H₅), sodiumphenoxide) and the like. Typically, this regeneration step furthercomprising or is followed by the step of washing the anionicpolyelectrolyte with a solvent or the diluent.

According to an aspect, the regenerative base 5 can be or can comprise anucleophilic base, for example a metal hydroxide or metal alkoxide.While the regenerative base 5 can comprise a non-nucleophilic base, theprocesses disclosed herein work in the absence of a non-nucleophilicbase such as an alkali metal hydride or an alkaline earth metal hydride,an alkali metal or alkaline earth metal dialkylamides and diarylamides,an alkali metal or alkaline earth metal hexalkyldisilazane, and analkali metal or alkaline earth metal dialkylphosphides anddiarylphosphides.

Typically, the inorganic bases such as alkali metal hydroxides or alkalimetal alkoxides have been found to work the best. However, in oneaspect, the reaction of Scheme 1 can be conducted using some bases butin the absence of certain other organic bases such as an alkoxide,aryloxide, amide, alkyl amide, arylamide, or the like. In anotheraspect, the anionic polyelectrolyte (and associated cations) can be usedand regenerated in the absence of an alkoxide or aryloxide. Further, thereactions and processes disclosed herein can be conducted in the absenceof an alkoxide, an aryloxide, an alkylamide, an arylamide, an amine, ahydride, a phosphazene, and/or substituted analogs thereof. For example,the processes disclosed herein can be conducted in the absence of sodiumhydride, an aryloxide salt (such as a sodium aryloxide), an alkoxidesalt (such as a sodium tert-butoxide), and/or a phosphazene.

The processes disclosed herein typically are conducted in the presenceof a diluent. Mixtures and combinations of diluents can be utilized inthese processes. The diluent can comprise, consist essentially of, orconsist of, any suitable solvent or any solvent disclosed herein, unlessotherwise specified. For example, the diluent can comprise, consistessentially of, or consist of a non-protic solvent, a protic solvent, anon-coordinating solvent, or a coordinating solvent. For instance, inaccordance with one aspect of this disclosure, the diluent can comprisea non-protic solvent. Representative and non-limiting examples ofnon-protic solvents can include tetrahydrofuran (THF), 2,5-Me₂THF,acetone, toluene, chlorobenzene, pyridine, carbon dioxide, olefin andthe like, as well as combinations thereof. In accordance with anotheraspect, the diluent can comprise a weakly coordinating ornon-coordinating solvent. Representative and non-limiting examples ofweakly coordinating or non-coordinating solvents can include toluene,chlorobenzene, paraffins, halogenated paraffins, and the like, as wellas combinations thereof.

In accordance with yet another aspect, the diluent can comprise acarbonyl-containing solvent, for instance, ketones, esters, amides, andthe like, as well as combinations thereof. Representative andnon-limiting examples of carbonyl-containing solvents can includeacetone, ethyl methyl ketone, ethyl acetate, propyl acetate, butylacetate, isobutyl isobutyrate, methyl lactate, ethyl lactate,N,N-dimethylformamide, and the like, as well as combinations thereof. Instill another aspect, the diluent can comprise THF, 2,5-Me₂THF,methanol, acetone, toluene, chlorobenzene, pyridine, anisole, or acombination thereof; alternatively, THF; alternatively, 2,5-Me₂THF;alternatively, methanol; alternatively, acetone; alternatively, toluene;alternatively, chlorobenzene; or alternatively, pyridine.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an aromatic hydrocarbon solvent. Non-limiting examples ofsuitable aromatic hydrocarbon solvents that can be utilized singly or inany combination include benzene, toluene, xylene (inclusive ofortho-xylene, meta-xylene, para-xylene, or mixtures thereof), andethylbenzene, or combinations thereof; alternatively, benzene;alternatively, toluene; alternatively, xylene; or alternatively,ethylbenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) a halogenated aromatic hydrocarbon solvent. Non-limitingexamples of suitable halogenated aromatic hydrocarbon solvents that canbe utilized singly or in any combination include chlorobenzene,dichlorobenzene, and combinations thereof; alternatively, chlorobenzene;or alternatively, dichlorobenzene.

In an aspect, the diluent can comprise (or consist essentially of, orconsist of) an ether solvent. Non-limiting examples of suitable ethersolvents that can be utilized singly or in any combination includedimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether,di-n-butyl ether, diphenyl ether, methyl ethyl ether, methyl t-butylether, dihydrofuran, tetrahydrofuran (THF), 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, anisole, and combinations thereof;alternatively, diethyl ether, dibutyl ether, THF, 2,5-Me₂THF,1,2-dimethoxyethane, 1,4-dioxane, and combinations thereof;alternatively, THF; or alternatively, diethyl ether.

In a further aspect, any of these aforementioned diluents can beexcluded from the diluent or diluent mixture. For example, the diluentcan be absent a phenol or a substituted phenol, an alcohol or asubstituted alcohol, an amine or a substituted amine, water, an ether,an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, analdehyde or ketone, an ester or amide, and/or absent a halogenatedaromatic hydrocarbon, or any substituted analogs of these diluentshalogenated analogs, including any of the aforementioned diluents.Therefore, Applicant reserves the right to exclude any of the diluentsprovided herein.

In all aspects and embodiments disclosed herein, the diluent can includeor comprise carbon dioxide, olefin, or combinations thereof. At least aportion of the diluent can comprise the α,β-unsaturated carboxylic acidor the salt thereof, formed in the process.

In this disclosure, the term transition metal precursor, transitionmetal compound, transition metal catalyst, transition metal precursorcompound, carboxylation catalyst, transition metal precursor complex andsimilar terms refer to a chemical compound that serves as the precursorto the metalalactone, prior to the coupling of the olefin and carbondioxide at the metal center of the transition metal precursor compound.Therefore, the metal of the transition metal precursor compound and themetal of the metalalactone are the same. In some aspects, some of theligands of the transition metal precursor compound carry over and areretained by the metalalactone following the coupling reaction. In otheraspects, the transition metal precursor compound loses its existingligands, referred to herein as first ligands, in presence of additionalligands such as chelating ligands, referred to herein as second ligands,as the metalalactone is formed. Therefore, the metalalactone generallyincorporates the second (added) ligand(s), though in some aspects, themetalalactone can comprise the first ligand(s) that were bound in thetransition metal precursor compound.

According to an aspect, the transition metal catalyst or compound usedin the processes can be used without being immobilized on a solidsupport. That is the transition metal catalyst can be used in its usualform which is soluble in most useful solvents, without being bonded toor supported on any insoluble support, such as an inorganic oxide ormixed oxide material.

A prototypical example of a transition metal precursor compound thatloses its initial ligands in the coupling reaction in the presence of asecond (added) ligand, wherein the metalalactone incorporates the second(added) ligand(s), is contacting Ni(COD)₂ (COD is 1,5-cyclooctadiene)with a diphosphine ligand such as 1,2-bis(dicyclohexylphosphino)ethanein a diluent in the presence of ethylene and CO₂ to form anickelalactone with a coordinated 1,2-bis(dicyclohexylphosphino)ethanebidentate ligand.

Accordingly, in an aspect, the process for producing an α,β-unsaturatedcarboxylic acid or a salt thereof, can comprise:

-   -   (1) contacting in any order        -   (a) a transition metal precursor compound comprising at            least one first ligand;        -   (b) optionally, at least one second ligand;        -   (c) an olefin;        -   (d) carbon dioxide (CO₂);        -   (e) a diluent; and        -   (f) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.

Generally, the processes disclosed herein employ a metalalactone or atransition metal precursor compound or complex. The transition metal ofthe metalalactone, or of the transition metal precursor compound, can bea Group 3 to Group 8 transition metal or, alternatively, a Group 8 toGroup 11 transition metal. In one aspect, for instance, the transitionmetal can be Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au, while inanother aspect, the transition metal can be Fe, Ni, or Rh.Alternatively, the transition metal can be Fe; alternatively, thetransition metal can be Co; alternatively, the transition metal can beNi; alternatively, the transition metal can be Cu; alternatively, thetransition metal can be Ru; alternatively, the transition metal can beRh; alternatively, the transition metal can be Pd; alternatively, thetransition metal can be Ag; alternatively, the transition metal can beIr; alternatively, the transition metal can be Pt; or alternatively, thetransition metal can Au.

In particular aspects contemplated herein, the transition metal can beNi. Hence, the metalalactone can be a nickelalactone and the transitionmetal precursor compound can be a Ni-ligand complex in these aspects.

The ligand of the metalalactone and/or of the transition metal precursorcompound, can be any suitable neutral electron donor group and/or Lewisbase. For instance, the suitable neutral ligands can include sigma-donorsolvents that contain a coordinating atom (or atoms) that can coordinateto the transition metal of the metalalactone (or of the transition metalprecursor compound). Examples of suitable coordinating atoms in theligands can include, but are not limited to, O, N, S, and P, orcombinations of these atoms. In some aspects consistent with thisdisclosure, the ligand can be a bidentate ligand.

In an aspect, the ligand used to form the metalalactone and/or thetransition metal precursor compound can be an ether, an organiccarbonyl, a thioether, an amine, a nitrile, or a phosphine. In anotheraspect, the ligand used to form the metalalactone or the transitionmetal precursor compound can be an acyclic ether, a cyclic ether, anacyclic organic carbonyl, a cyclic organic carbonyl, an acyclicthioether, a cyclic thioether, a nitrile, an acyclic amine, a cyclicamine, an acyclic phosphine, or a cyclic phosphine.

Suitable ethers can include, but are not limited to, dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methylpropyl ether, methyl butyl ether, diphenyl ether, ditolyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran,dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran,3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane,morpholine, and the like, including substituted derivatives thereof.

Suitable organic carbonyls can include ketones, aldehydes, esters, andamides, either alone or in combination, and illustrative examples caninclude, but are not limited to, acetone, acetophonone, benzophenone,N,N-dimethylformamide, N,N-dimethylacetamide, methyl acetate, ethylacetate, and the like, including substituted derivatives thereof.

Suitable thioethers can include, but are not limited to, dimethylthioether, diethyl thioether, dipropyl thioether, dibutyl thioether,methyl ethyl thioether, methyl propyl thioether, methyl butyl thioether,diphenyl thioether, ditolyl thioether, thiophene, benzothiophene,tetrahydrothiophene, thiane, and the like, including substitutedderivatives thereof.

Suitable nitriles can include, but are not limited to, acetonitrile,propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, andthe like, including substituted derivatives thereof.

Suitable amines can include, but are not limited to, methyl amine, ethylamine, propyl amine, butyl amine, dimethyl amine, diethyl amine,dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine,tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine,tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole,indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole,2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole,2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole,3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3,4-dibutylpyrrole,2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole,3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole,3-ethyl-2,4-dimethylpyrrole, 2,3,4,5-tetramethylpyrrole,2,3,4,5-tetraethylpyrrole, 2,2′-bipyridine,1,8-Diazabicyclo[5.4.0]undec-7-ene, di(2-pyridyl)dimethylsilane,N,N,N′,N′-tetramethylethylenediamine, 1,10-phenanthroline,2,9-dimethyl-1,10-phenanthroline, glyoxal-bis(mesityl)-1,2-diimine andthe like, including substituted derivatives thereof. Suitable amines canbe primary amines, secondary amines, or tertiary amines.

Suitable phosphines and other phosphorus compounds can include, but arenot limited to, trimethylphosphine, triethylphosphine,tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine,diphenylphosphine, ditolylphosphine, triphenylphosphine,tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine,ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine,trimethyl phosphite, triethyl phosphite, tripropyl phosphite,triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite,2-(di-t-butylphosphino)biphenyl, 2-di-t-butylphosphino-1,1′-binaphthyl,2-(di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-di-t-butylphosphino-2′-methylbiphenyl,2-(di-t-butylphosphinomethyl)pyridine,2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,1′-biphenyl,2-(dicyclohexylphosphino)biphenyl,(S)-(+)-(3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a′]dinaphthalen-4-yl)dimethylamine,2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl,1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP),1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)-ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutyl-phosphino)ethane, 1,2-bis(di-t-butyl-phosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane,1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane, 1,3-bis(diphenylphosphino)propane,1,3-bis(di-t-butylphosphino)propane,1,4-bis(diisopropylphosphino)butane, 1,4-bis(diphenylphosphino)butane,2,2′-bis[bis(3,5-dimethylphenyl)phosphino]-4,4′,6,6′-tetramethoxybiphenyl,2,6-bis(di-t-butylphosphinomethyl)pyridine,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,bis(2-dicyclohexylphosphinophenyl)ether,5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole,2-t-butylphosphinomethylpyridine, bis(diphenylphosphino)ferrocene,bis(diphenylphosphino)methane, bis(dicyclohexylphosphino)methane,bis(di-t-butylphosphino)methane, and the like, including substitutedderivatives thereof.

In other aspects, the ligand used to form the metalalactone or thetransition metal precursor compound can be a carbene, for example, aN-heterocyclic carbene (NHC) compound. Representative and non-limitingexamples of suitable N-heterocyclic carbene (NHC) materials include thefollowing:

Illustrative and non-limiting examples of metalalactone complexes(representative nickelalactones) suitable for use as described hereininclude the following compounds (Cy=cyclohexyl, ^(t)Bu=tert-butyl):

The transition metal precursor compounds corresponding to theseillustrative metalalactones are shown below:

Metalalactones can be synthesized according to the following generalreaction scheme (illustrated with nickel as the transition metal;Ni(COD)₂ is bis(1,5-cyclooctadiene)nickel(0)):

and according to suitable procedures well known to those of skill in theart.

Suitable ligands, transition metal precursor compounds, andmetalalactones are not limited solely to those ligands, transition metalprecursor compounds, and metalalactones disclosed herein. Other suitableligands, transition metal precursor compounds, and metalalactones aredescribed, for example, in U.S. Pat. Nos. 7,250,510, 8,642,803, and8,697,909; Journal of Organometallic Chemistry, 1983, 251, C51-C53; Z.Anorg. Allg. Chem., 1989, 577, 111-114; Journal of OrganometallicChemistry, 2004, 689, 2952-2962; Organometallics, 2004, Vol. 23,5252-5259; Chem. Commun., 2006, 2510-2512; Organometallics, 2010, Vol.29, 2199-2202; Chem. Eur. J., 2012, 18, 14017-14025; Organometallics,2013, 32 (7), 2152-2159; and Chem. Eur. J., 2014, Vol. 20, 11,3205-3211; the disclosures of which are incorporated herein by referencein their entirety.

Generally, the features of the processes disclosed herein (e.g., themetalalactone, the diluent, the anionic polyelectrolyte, theα,β-unsaturated carboxylic acid or salt thereof, the transition metalprecursor compound, the olefin, and the conditions under which theα,β-unsaturated carboxylic acid, or a salt thereof, is formed, amongothers) are independently described, and these features can be combinedin any combination to further describe the disclosed processes.

In accordance with an aspect of the present disclosure, a process forperforming a metalalactone elimination reaction is disclosed, in whichthe process forms an α,β-unsaturated carboxylic acid or salt thereof.This process can comprise (or consist essentially of, or consist of):

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to        induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or a salt thereof.        Suitable metalalactones, diluents, and anionic polyelectrolytes        are disclosed hereinabove. In this process for performing a        metalalactone elimination reaction, for instance, at least a        portion of the diluent can comprise the α,β-unsaturated        carboxylic acid, or the salt thereof, that is formed in step (2)        of this process.

In accordance with another aspect of the present disclosure, a processfor producing an α,β-unsaturated carboxylic acid, or a salt thereof, isdisclosed. This process can comprise (or consist essentially of, orconsist of):

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture comprising an adduct            of the metalalactone and the anionic polyelectrolyte and its            associated metal cations; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.        In this process for producing an α,β-unsaturated carboxylic acid        or a salt thereof, for instance, at least a portion of the        diluent of the reaction mixture comprising the adduct of the        metalalactone can be removed after step (1), and before step        (2), of this process. Suitable metalalactones, diluents, and        anionic polyelectrolytes are disclosed hereinabove.

As discussed further in this disclosure, the above processes can furthercomprise a step of contacting a transition metal precursor compoundcomprising at least one first ligand, an olefin, and carbon dioxide(CO₂) to form the metalalactone comprising at least one ligand. That is,at least one ligand of the transition metal precursor compound can becarried over to the metalalactone. In further aspects, the aboveprocesses can further comprise a step of contacting a transition metalprecursor compound comprising at least one first ligand with at leastone second ligand, an olefin, and carbon dioxide (CO₂) to form themetalalactone comprising at least one ligand. In this aspect, the ligandset of the metalalactone typically comprises the at least one secondligand. That is, the metalalactone ligand can comprise the at least onefirst ligand, the at least one second ligand, or a combination thereof.

In some aspects, the contacting step—step (1)—of the above processes caninclude contacting, in any order, the metalalactone, the diluent, andthe anionic polyelectrolyte, and additional unrecited materials. Inother aspects, the contacting step can consist essentially of, orconsist of, the metalalactone, the diluent, and the anionicpolyelectrolyte components. Likewise, additional materials or featurescan be employed in the applying conditions step—step (2)—that forms orproduces the α,β-unsaturated carboxylic acid, or the salt thereof.Further, it is contemplated that these processes for producing anα,β-unsaturated carboxylic acid or a salt thereof by a metalalactoneelimination reaction can employ more than one metalalactone and/or morethan one anionic polyelectrolyte. Additionally, a mixture or combinationof two or more diluents can be employed.

Any suitable reactor, vessel, or container can be used to contact themetalalactone, diluent, and anionic polyelectrolyte, non-limitingexamples of which can include a flow reactor, a continuous reactor, afixed bed reactor, a moving reactor bed, and a stirred tank reactor,including more than one reactor in series or in parallel, and includingany combination of reactor types and arrangements. In particular aspectsconsistent with this disclosure, the metalalactone and the diluent cancontact a fixed bed of the anionic polyelectrolyte, for instance, in asuitable vessel, such as in a continuous fixed bed reactor. In furtheraspects, combinations of more than one anionic polyelectrolyte can beused, such as a mixed bed of a first anionic polyelectrolyte and asecond anionic polyelectrolyte, or sequential beds of a first anionicpolyelectrolyte and a second anionic polyelectrolyte. In these and otheraspects, the feed stream can flow upward or downward through the fixedbed. For instance, the metalalactone and the diluent can contact thefirst anionic polyelectrolyte and then the second anionicpolyelectrolyte in a downward flow orientation, and the reverse in anupward flow orientation. In a different aspect, the metalalactone andthe anionic polyelectrolyte can be contacted by mixing or stirring inthe diluent, for instance, in a suitable vessel, such as a stirred tankreactor.

Step (1) of the process for producing an α,β-unsaturated carboxylic acidor a salt thereof also recites forming an adduct of the metalalactoneand the anionic polyelectrolyte and its associated metal cations.Without intending to be bound by theory, there is some interactionbetween the metalalactone and the anionic polyelectrolyte and itsassociated metal cations that are believed to destabilize themetalalactone for its elimination of the metal acrylate. Thisinteraction can be referred to generally as an adduct of themetalalactone and the anionic polyelectrolyte or an adduct of theα,β-unsaturated carboxylic acid with the anionic polyelectrolyte. Thisadduct can contain all or a portion of the α,β-unsaturated carboxylicacid and can be inclusive of salts of the α,β-unsaturated carboxylicacid.

Accordingly, applying conditions to the reaction mixture suitable toform an α,β-unsaturated carboxylic acid or a salt thereof is intended toreflect any concomitant or subsequent conditions to step (1) of theabove processes that release the α,β-unsaturated carboxylic acid or asalt thereof from the adduct, regardless of the specific nature of theadduct.

For example, in step (2) of the process of applying conditions to thereaction mixture suitable to form an α,β-unsaturated carboxylic acid ora salt thereof, the adduct of the metalalactone and the anionicpolyelectrolyte and its associated metal cations as defined herein issubjected to some chemical or other conditions or treatment to producethe α,β-unsaturated carboxylic acid or its salt. Various methods can beused to liberate the α,β-unsaturated carboxylic acid or its salt, fromthe anionic polyelectrolyte. In one aspect, for instance, the treatingstep can comprise contacting the adduct of the metalalactone and theanionic polyelectrolyte and its associated metal cations with an acid.Representative and non-limiting examples of suitable acids can includeHCl, acetic acid, and the like, as well as combinations thereof. Inanother aspect, the treating step can comprise contacting the adduct ofthe metalalactone and the anionic polyelectrolyte and its associatedmetal cations with a base. Representative and non-limiting examples ofsuitable bases can include carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃),hydroxides (e.g., Mg(OH)₂, Na(OH), alkoxides (e.g., Al(O^(i)Pr)₃,Na(O^(t)Bu), Mg(OEt)₂), and the like, as well as combinations thereof(^(i)Pr=isopropyl, ^(t)Bu=tert-butyl, Et=ethyl). In yet another aspect,the treating step can comprise contacting the adduct of themetalalactone and the anionic polyelectrolyte and its associated metalcations with a suitable solvent. Representative and non-limitingexamples of suitable solvents can include carbonyl-containing solventssuch as ketones, esters, amides, etc. (e.g., acetone, ethyl acetate,N,N-dimethylformamide, etc., as described herein above), alcoholsolvents, water, and the like, as well as combinations thereof.

In still another aspect, the treating step can comprise heating theadduct of the metalalactone and the anionic polyelectrolyte and itsassociated metal cations to any suitable temperature. This temperaturecan be in a range, for example, from 50 to 1000° C., from 100 to 800°C., from 150 to 600° C., from 250 to 1000° C., from 250° C. to 550° C.,or from 150° C. to 500° C. The duration of this heating step is notlimited to any particular period of time, as long of the period of timeis sufficient to liberate the α,β-unsaturated carboxylic acid from theanionic polyelectrolyte. As those of skill in the art recognize, theappropriate treating step depends upon several factors, such as theparticular diluent used in the process, and the particular anionicpolyelectrolyte used in the process, amongst other considerations. Onefurther treatment step can comprise, for example, a workup step withadditional olefin to displace an alkene-nickel bound acrylate.

In these processes for performing a metalalactone elimination reactionand for producing an α,β-unsaturated carboxylic acid (or a saltthereof), additional process steps can be conducted before, during,and/or after any of the steps described herein. As an example, theseprocesses can further comprise a step (e.g., prior to step (1)) ofcontacting a transition metal precursor compound with an olefin andcarbon dioxide to form the metalalactone. Transition metal precursorcompounds are described hereinabove. Illustrative and non-limitingexamples of suitable olefins can include ethylene, propylene, butene(e.g., 1-butene), pentene, hexene (e.g., 1-hexene), heptane, octene(e.g., 1-octene), and styrene and the like, as well as combinationsthereof.

Yet, in accordance with another aspect of the present disclosure, aprocess for producing an α,β-unsaturated carboxylic acid, or a saltthereof, is disclosed. This process can comprise (or consist essentiallyof, or consist of):

-   -   (1) contacting in any order        -   (a) a transition metal precursor compound comprising at            least one first ligand;        -   (b) optionally, at least one second ligand;        -   (c) an olefin;        -   (d) carbon dioxide (CO₂);        -   (e) a diluent; and        -   (f) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to form        an α,β-unsaturated carboxylic acid or a salt thereof.

In aspects of this process that utilizes a transition metal precursorcompound comprising at least one first ligand, the olefin can beethylene, and the step of contacting a transition metal precursorcompound with an olefin and carbon dioxide (CO₂) can be conducted usingany suitable pressure of ethylene, or any pressure of ethylene disclosedherein, e.g., from 10 psig (70 KPa) to 1,000 psig (6,895 KPa), from 25psig (172 KPa) to 500 psig (3,447 KPa), or from 50 psig (345 KPa) to 300psig (2,068 KPa), and the like. Further, the olefin can be ethylene, andthe step of contacting a transition metal precursor compound with anolefin and carbon dioxide (CO₂) can be conducted using a constantaddition of the olefin, a constant addition of carbon dioxide, or aconstant addition of both the olefin and carbon dioxide, to provide thereaction mixture. By way of example, in a process wherein the ethyleneand carbon dioxide (CO₂) are constantly added, the process can utilizean ethylene:CO₂ molar ratio of from 5:1 to 1:5, from 3:1 to 1:3, from2:1 to 1:2, or about 1:1, to provide the reaction mixture.

According to a further aspect of the above process that utilizes atransition metal precursor compound, the process can include the step ofcontacting a transition metal precursor compound with an olefin andcarbon dioxide (CO₂) conducted using any suitable pressure of CO₂, orany pressure of CO₂ disclosed herein, e.g., from 20 psig (138 KPa) to2,000 psig (13,790 KPa), from 50 psig (345 KPa) to 750 psig (5,171 KPa),or from 100 psig (689 KPa) to 300 psig (2,068 KPa), and the like. In anyof the processes disclosed herein, the processes can further comprise astep of monitoring the concentration of at least one reaction mixturecomponent, at least one elimination reaction product, or a combinationthereof, for any reason, such as to adjust process parameters in realtime, to determine extent or reaction, or to stop the reaction at thedesired point.

As illustrated, this process that utilizes a transition metal precursorcompound comprising at least one first ligand includes one aspect inwhich no second ligand is employed in the contacting step, and anotheraspect in which a second ligand is used in the contacting step. That is,one aspect involves the contacting step of the process comprisingcontacting the transition metal precursor compound comprising at leastone first ligand with the at least one second ligand. The order ofcontacting can be varied. For example, the contacting step of theprocess disclosed above can comprise contacting (a) the transition metalprecursor compound comprising at least one first ligand with (b) the atleast one second ligand to form a pre-contacted mixture, followed bycontacting the pre-contacted mixture with the remaining components(c)-(f) in any order to provide the reaction mixture.

Further embodiments related to the order of contacting, for example, thecontacting step can include or comprise contacting the metalalactone,the diluent, and the anionic polyelectrolyte in any order. Thecontacting step can also comprise contacting the metalalactone and thediluent to form a first mixture, followed by contacting the firstmixture with the anionic polyelectrolyte to form the reaction mixture.In a further aspect, the contacting step can comprise contacting thediluent and the anionic polyelectrolyte to form a first mixture,followed by contacting the first mixture with the metalalactone to formthe reaction mixture. In yet a further aspect, the contacting step ofthe process can further comprise contacting any number of additives, forexample, additives that can be selected from an acid, a base, or areductant.

Suitable transition metal-ligands, olefins, diluents, anionicpolyelectrolytes with associated metal cations are disclosedhereinabove. In some aspects, the contacting step—step (1)—of thisprocess can include contacting, in any order, the transitionmetal-ligand, the olefin, the diluent, the anionic polyelectrolyte andcarbon dioxide, and additional unrecited materials. In other aspects,the contacting step can consist essentially of, or consist of,contacting, in any order, the transition metal-ligand, the olefin, thediluent, the anionic polyelectrolyte, and carbon dioxide. Likewise,additional materials or features can be employed in the forming step ofstep (2) of this process. Further, it is contemplated that thisprocesses for producing an α,β-unsaturated carboxylic acid, or a saltthereof, can employ more than one transition metal-ligand complex and/ormore than one anionic polyelectrolyte if desired and/or more than oneolefin. Additionally, a mixture or combination of two or more diluentscan be employed.

As above, any suitable reactor, vessel, or container can be used tocontact the transition metal-ligand, olefin, diluent, anionicpolyelectrolyte, and carbon dioxide, whether using a fixed bed of theanionic polyelectrolyte, a stirred tank for contacting (or mixing), orsome other reactor configuration and process. While not wishing to bebound by the following theory, a proposed and illustrative reactionscheme for this process is provided below.

Independently, the contacting and forming steps of any of the processesdisclosed herein (i.e., for performing a metalalactone eliminationreaction, for producing an α,β-unsaturated carboxylic acid, or a saltthereof), can be conducted at a variety of temperatures, pressures, andtime periods. For instance, the temperature at which the components instep (1) are initially contacted can be the same as, or different from,the temperature at which the forming step (2) is performed. As anillustrative example, in the contacting step, the components can becontacted initially at temperature T1 and, after this initial combining,the temperature can be increased to a temperature T2 for the formingstep (e.g., to form the α,β-unsaturated carboxylic acid, or the saltthereof). Likewise, the pressure can be different in the contacting stepand the forming step. Often, the time period in the contacting step canbe referred to as the contact time, while the time period in formingstep can be referred to as the reaction time. The contact time and thereaction time can be, and often are, different.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein can be conducted at a temperature in a rangefrom 0° C. to 250° C.; alternatively, from 20° C. to 200° C.;alternatively, from 0° C. to 95° C.; alternatively, from 10° C. to 75°C.; alternatively, from 10° C. to 50° C.; or alternatively, from 15° C.to 70° C. In these and other aspects, after the initial contacting, thetemperature can be changed, if desired, to another temperature for theforming step. These temperature ranges also are meant to encompasscircumstances where the contacting step and/or the forming step can beconducted at a series of different temperatures, instead of at a singlefixed temperature, falling within the respective ranges.

In an aspect, the contacting step and/or the forming step of theprocesses disclosed herein can be conducted at a pressure in a rangefrom 5 (34 KPa) to 10,000 psig (68,948 KPa), such as, for example, from5 psig (34 KPa) to 2500 psig (17,237 KPa). In some aspects, the pressurecan be in a range from 5 psig (34 KPa) to 500 psig (3,447 KPa);alternatively, from 25 psig (172 KPa) to 3000 psig (20,684 KPa);alternatively, from 45 psig (310 KPa) to 1000 psig (6,895 KPa); oralternatively, from 50 psig (345 KPa) to 250 psig (1,724 KPa).

The contacting step of the processes is not limited to any particularduration of time. That is, the respective components can be initiallycontacted rapidly, or over a longer period of time, before commencingthe forming step. Hence, the contacting step can be conducted, forexample, in a time period ranging from as little as 1-30 seconds to aslong as 1-12 hours, or more. In non-continuous or batch operations, theappropriate reaction time for the forming step can depend upon, forexample, the reaction temperature, the reaction pressure, and the ratiosof the respective components in the contacting step, among othervariables. Generally, however, the forming step can occur over a timeperiod that can be in a range from 1 minute to 96 hours, such as, forexample, from 2 minutes to 96 hours, from 5 minutes to 72 hours, from 10minutes to 72 hours, or from 15 minutes to 48 hours.

If the process employed is a continuous process, then themetalalactone/anionic electrolyte catalyst contact/reaction time (or thetransition metal-ligand/anionic electrolyte catalyst contact/reactiontime) can be expressed in terms of weight hourly space velocity(WHSV)—the ratio of the weight of the metalalactone (or transitionmetal-ligand complex) which comes in contact with a given weight ofanionic electrolyte per unit time (for example, hr⁻¹). While not limitedthereto, the WHSV employed, based on the amount of the anionicelectrolyte, can be in a range from 0.05 to 100 hr⁻¹, from 0.05 to 50hr⁻¹, from 0.075 to 50 hr⁻¹, from 0.1 to 25 hr⁻¹, from 0.5 to 10 hr⁻¹,from 1 to 25 hr⁻¹, or from 1 to 5 hr⁻¹.

In the processes disclosed herein, the molar yield of theα,β-unsaturated carboxylic acid, or the salt thereof), based on themetalalactone (or the transition metal-ligand complex) is at least 2%,and more often can be at least 5%, at least 10%, or at least 15%. Inparticular aspects of this disclosure, the molar yield can be at least18%, at least 20%, at least 25%, at least 35%, at least 50%, at least60%, at least 75%, or at least 85%, or at least 90%, or at least 95%, orat least 100%. That is, catalytic formation of the α,β-unsaturatedcarboxylic acid or the salt thereof can be effected with the disclosedsystem. For example, the molar yield of the α,β-unsaturated carboxylicacid, or the salt thereof, based on the metalalactone or based on thetransition metal precursor compound can be at least 20%, at least 40%,at least 60%, at least 80%, at least 100%, at least 120%, at least 140%,at least 160%, at least 180%, at least 200%, at least 250%, at least300%, at least 350%, at least 400%, at least 450%, or at least 500%.

The specific α,β-unsaturated carboxylic acid (or salt thereof) that canbe formed or produced using the processes of this disclosure is notparticularly limited. Illustrative and non-limiting examples of theα,β-unsaturated carboxylic acid can include acrylic acid, methacrylicacid, 2-ethylacrylic acid, cinnamic acid, and the like, as well ascombinations thereof. Illustrative and non-limiting examples of the saltof the α,β-unsaturated carboxylic acid can include sodium acrylate,potassium acrylate, magnesium acrylate, sodium (meth)acrylate, and thelike, as well as combinations thereof.

Once formed, the α,β-unsaturated carboxylic acid (or salt thereof) canbe purified and/or isolated and/or separated using suitable techniqueswhich can include, but are not limited to, evaporation, distillation,chromatography, crystallization, extraction, washing, decanting,filtering, drying, and the like, including combinations of more than oneof these techniques. In an aspect, the process for performing ametalalactone elimination reaction (or the process for producing anα,β-unsaturated carboxylic acid, or a salt thereof) can further comprisea step of separating or isolating the α,β-unsaturated carboxylic acid(or salt thereof) from other components, e.g., the diluent, the anionicelectrolyte, and the like.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

General Considerations

Unless otherwise noted, all operations were performed under purifiednitrogen or vacuum using standard Schlenk or glovebox techniques.Toluene (Honeywell) and tetrahydrofuran (Aldrich) was degassed and driedover activated 4 Å molecular sieves under nitrogen. Sodiumtert-butoxide, potassium tert-butoxide, poly(4-vinylphenol)(M_(w)˜11,000 g/mol), poly(4-vinylphenol-co-methyl(meth)acrylate)(M_(w)˜8,000-12,000 g/mol), and brominated poly(4-vinylphenol)(M_(w)˜5,800 g/mol) were purchased from Sigma-Aldrich and used asreceived. Phenol/formaldehyde resin was purchased as hollow beads(˜5-127 μm) from Polysciences, Inc. Bis(1,5-cyclooctadiene)nickel(0) and1,2-Bis(dicyclohexylphosphino)ethane were purchased from Strem and wereused as received. (TMEDA)Ni(CH₂CH₂CO₂) was prepared according toliterature procedures (Fischer, R; Nestler, B., and Schutz, H. Z. anorg.allg. Chem. 577 (1989) 111-114).

Preparation of Compounds

Sodium poly(4-vinylphenol). To sodium tert-butoxide (15 g, 125 mmol) andpoly(4-vinylphenol) (12 g, 125 mmol) was added toluene (600 mL) in a 1 Lround-bottomed flask equipped with a stirbar. The mixture was stirredfor four days then frit filtered. The filter cake was washed with 30 mLof toluene followed by 15 mL of toluene, then allowed to dry. The drycake was washed with 3×20 mL of toluene leaving a solid.

Potassium poly(4-vinylphenol). Prepared analogously to sodiumpoly(4-vinylphenol) substituting potassium tert-butoxide for sodiumtert-butoxide.

Sodium poly(4-vinylphenol-co-methyl(meth)acrylate). Prepared analogouslyto sodium poly(4-vinylphenol) substitutingpoly(4-vinylphenol-co-methyl(meth)acrylate) for poly(4-vinylphenol).

Sodium poly(4-vinylphenol), brominated. Prepared analogously to sodiumpoly(4-vinylphenol) substituting poly(4-vinylphenol), brominated forpoly(4-vinylphenol).

Sodium phenol/formaldehyde resin. Phenolic resin (phenol/formaldehyderesin) was suspended in a solution of sodium hydroxide in either wateror methanol and stirred at 55° C. overnight prior to filtration, andsubsequently washed with copious amounts of the solvent in which it wastreated. The solid was then dried under vacuum prior to storage undernitrogen.

Examples 1-10 Experimental Procedure for Ethylene/Carbon DioxideCoupling

The ethylene/carbon dioxide reaction of these examples is set out inreaction (1) below, and specific reagents, reaction conditions, andyields are set out in Table 1.

A 1-liter autoclave pressure reactor was charged with solvent followedby a combined mixture of Ni(COD)₂ (0.10 mmol),bis(dicyclohexylphosphino)ethane (0.11 mmol), and poly(4-vinylphenoxide)(1.00 g) in 10 mL of solvent. The reactor was set to 50° C., pressurizedwith ethylene at the desired level, and equilibrated for 5-10 minutes(min) prior to being pressurized and equilibrated with carbon dioxide.The reactor was then set to 100° C. and stirred for 6 hours. After thisreaction time, and after cooling to ambient temperature, the reactor wasslowly vented and the mixture was collected. The solvent was removed invacuo and the residue was stirred in 10-20 mL of deuterium oxide for 30min prior to the addition of a sorbic acid/acetone-d₆ solution. Themixture was filtered and analyzed by NMR (sorbic acid is used as theinternal standard) for acrylate yield determination.

TABLE 1 Ethylene/carbon dioxide coupling and acrylate yields [Sol-Acrylate vent] [C₂H₄] [CO₂] Yield Example M Solvent (mL) (psi (KPa))(psi (KPa) (%) 1 Na Toluene 300 150 100 14 (1,034)   (689) 2 K Toluene300 100 150 68 (689) (1,034)   3 K Toluene 300 150 300 117 (1,034)  (2,068)   4 K Toluene 50 150 300 42 (1,034)   (2,068)   5 K Toluene 50 75 300 25 (517) (2,068)   6 Na Toluene 300 150 300 104 (1,034)  (2,068)   7 Na^(A) Toluene 300 150 300 130 (1,034)   (2,068)   8 NaToluene 50 150 300 23 (1,034)   (2,068)   9 Na THF 50 150 300 52(1,034)   (2,068)   10 Na THF 300 150 300 62 (1,034)   (2,068)  ^(A)2.00 g of poly(4-vinylphenoxide) were used in this example.

Examples 11-17 Experimental Procedure for Nickelalactone Conversion toAcrylate

To study the elimination step of the disclosed process, the efficienciesof various alkoxides or aryloxides for the conversion of adiphosphine-stabilized nickelalactone to acrylic acid were assessed.Specifically, the following experiments show the efficiencies of sodiumand potassium (4-vinylphenoxide) for the conversion of an in situprepared diphosphine-stabilized nickelalactone, and the data werecompared to the conversion using molecular sodium tert-butoxide foracrylate formation from the analogous nickelalactones. The metalalactoneto acrylate conversion reaction of these examples is set out in reaction(2) below, and specific reagents, reaction conditions, and yields areset out in Table 2. In reaction (2), the “metal alkoxide” includes thepolymeric alkoxides shown in Table 2.

In a 10 mL vial, (TMEDA)Ni(CH₂CH₂CO₂) (0.018 mmol),bis(dicyclohexylphosphino)-ethane (0.018 mmol), poly(4-vinylphenoxide),and solvent (5 mL) were combined and stirred at 60° C. for 30-60 min.Following removal of solvent, the solid residue was taken up in D₂O (3-5mL) for 30 min and filtered. An aliquot of a prepared sorbicacid/acetone-d₆ solution was added for determination of acrylic acidyield by NMR.

TABLE 2 Nickelalactone conversion to acrylate and acrylate yields [MetalAlkoxide] % Example Metal Alkoxide Solvent (mg) Yield 11 Sodiumpoly(4-vinylphenoxide) Toluene 100 33 12 Sodium poly(4-vinylphenoxide)Toluene 250 32 13 Sodium poly(4-vinylphenoxide) Toluene 25 15 14Potassium poly(4- Toluene 100 24 vinylphenoxide) 15 Sodiumpoly(4-vinylphenol-co- Toluene 100 66 methyl(meth)acrylate) 16 Sodiumpoly(4-vinylphenol), Toluene 100 6 brominated 17 Sodium tert-butoxideTHF 7 16

The study from Table 2 reveals, among other things, that increasing thesodium poly(4-vinylphenoxide) amount from 100 mg to 250 mg (Examples 11and 12) provides the same overall yield of the sodium acrylate/acrylicacid. Using the potassium salt (Example 14) as compared to the sodiumsalt (Example 11) of the poly(4-vinylphenoxide) somewhat lowered theyield of the sodium acrylate/acrylic acid.

Accordingly, this disclosure demonstrates at least the following: 1) afacile acid-base reaction that affords a metal polyvinylphenoxide orvarients thereof in excellent yields with negligible byproducts; 2) anickelalactone destabilization and cleavage that can proceed insurprisingly short time frames, that is, shorter times than expected (<1hour); and 3) the increased loadings of metal polyvinylphenoxide doesnot diminish the resulting yield of the acrylate/acrylic acid.

Example 18 Polymeric Stationary Phases for Catalytic Acrylate Formation

The present disclosure also provides for using polymeric stationaryphases, such as polyphenol resins (e.g. poly(4-vinylphenolate) resins)or polyaromatic resins (e.g. phenol-formaldehyde resins) in a column orother suitable solid state configuration, in which formation of theacrylate from a metalalactone (such as a nickelalactone) in a mobilephase can be effected.

FIG. 1 illustrates one way in which a polymeric stationary phasecatalyst column can be configured, in which the coupling reaction andelution of the metal acrylate from the column can be carried out. Asshown, a metal (e.g. sodium) poly(4-vinylphenolate) resins were found tobe suitable anionic polyelectrolyte promoters or “co-catalysts” in theconversion of olefin/carbon dioxide-derived nickelalactoneintermediates. This method can provide both easier separation ofacrylate from other materials and ease of regeneration of the polymericsupport materials to its salt form, such as sodiumpoly(4-vinylphenoxide).

Example 19-21 Sodium-Treated Crosslinked Polyaromatic Resins asStoichiometric Co-Catalysts in Olefin/Carbon Dioxide Conversion toα,β-Unsaturated Carboxylates

Because the metal (e.g. sodium) poly(4-vinylphenolate) resins were foundto be suitable promoters and sources of cations in the conversion ofolefin and carbon dioxide-derived nickelalactone intermediates, anevaluation of their crosslinked analogues was undertaken. It wasbelieved that these crosslinked polyaromatic resins would besufficiently insoluble in many commercial diluents to be applicabilityas a polymeric promoters and cation sources in a fixed bed/columnreactor setting. This method further allows for the potentialregeneration of the spent solid co-catalyst in both aqueous (forexample, sodium hydroxide in water) and/or organic media (for example,sodium alkoxide in toluene).

The following reaction (3) illustrates the conversion reaction of anolefin and carbon dioxide-derived nickelalactone intermediate that wasundertaken to evaluate some crosslinked polyelectrolyte analogues.Reaction conditions for reaction (3) are: 0.10 mmol [Ni], 0.11 mmoldiphosphine ligand, 500 mL of toluene, 1.0 g of sodium-treated,crosslinked polyaromatic resin (solid activator). The reactor wasequilibrated to 150 psi of ethylene followed by 300 psi of carbondioxide prior to heating. The yield reported in Table 3 was determinedby ¹H NMR spectroscopy in a D₂O/(CD₃)₂CO mixture relative to a sorbicacid standard.

The following table describe various examples where commercialpolyaromatic resins, which were either further treated with a sodiumbase under appropriate conditions or are commercially available in thesodium form, were found to be effective in the nickel-mediated synthesisof sodium acrylate from ethylene and carbon dioxide.

TABLE 3 Nickel-mediated conversion of carbon dioxide and ethylene tosodium acrylate with sodium treated polyaromatics.^(A) Base & AcrylateCo-catalyst Sodium [Solid]:[Na] yield Example Solvent Solid Source (wt)(%) 19 toluene Phenol/ NaOH 0.3 1.8 Formaldehyde (MeOH) 20 toluenePhenol/ NaOH (aq) 0.3 6.0 Formaldehyde 21 toluene Phenol/ NaO-t-Bu 1.0n.d.^(B) Formaldehyde ^(A)Reaction Conditions: 0.10 mmol [Ni], 0.11 mmoldiphosphine ligand, 500 mL toluene, 1.0 g solid activator(phenol-formaldehyde resin). Reactor was equilibrated to 150 psiethylene followed by 300 psi carbon dioxide prior to heating. Yielddetermined by ¹H NMR spectroscopy in D₂O/(CD₃)₂CO mixture relative tosorbic acid standard. ^(B)None detected.

Even though the yields of acrylate when employing these sodium-treatedcrosslinked resins may be modest, the data indicate that thenickel-mediated conversion of carbon dioxide and ethylene to sodiumacrylate with sodium treated crosslinked polyaromatic resins can becarried out. Further, the insolubilities of these resins in manycommercial solvents will allow for their utility in fixed bed/columnconfigurations.

The phenol/formaldehyde resins can be treated with sodium hydroxide toproduce what are believed to be sodium aryloxide sites that are activefor promoting nickelalactone scission, and more so when the NaOH isdissolved in water to provide a higher solubility (Example 20) versusmethanol (Example 19).

Example 21 Crosslinked Polyaromatic Resin Co-Catalysts in Olefin/CarbonDioxide Conversion to α,β-Unsaturated Carboxylates, Using Co-Monomers

In this example, co-monomer phenol compounds are used together withformaldehyde to prepare the crosslinked polyaromatic resins for use asdescribed according to the disclosure. The resin was prepared using theco-monomer combination of resorcinol (m-dihydroxybenzene) and2-fluorophenol monomer with formaldehyde, and the resulting resin wassodium-treated (NaOH, dissolved in water or alcohol) to generate theanionic polyelectrolyte, according to equation (4).

The polyaromatic resin is thought to act as a co-catalyst upon treatmentwith sodium hydroxide because of what are believed to be sodiumaryloxide sites that promote nickelalactone scission. It is noted thatincreased crosslink density is obtained using longer drying times toremove trapped excess water.

Examples 22-25 Additional Stationary Phases for Catalytic AcrylateFormation

The present disclosure also provides for using other polymericstationary phases and modifications thereof, for example, in a column orother suitable solid state configuration. Further variations of thistechnology include but are not limited to the following examples.

Example 22

Polymer modifications that include acid-base reaction being effectedusing a wide range of metal bases, including alkali and alkalinehydroxides, alkoxides, aryloxides, amides, alkyl or aryl amides, and thelike, such that an assortment of electrophiles can be used innickelalactone destabilization as demonstrated herein for thepolyvinylphenols.

Example 23

Polymer modifications can also include using variants of thepolyvinylphenol, that can be prepared by polymerization ofhydroxyl-substituted styrenes having a variety of organic and inorganicsubstituents, such as alkyls, halogens, and heteroatom substituents.

Example 24

Polymer modifications can also include using co-polymers based on, forexample, the co-polymerization of a protected hydroxyl-substitutedstyrene (such as acetoxystyrene) with other styrenes and (meth)acrylates(typically followed by hydrolysis to generate the polyvinylphenolco-polymer) to produce libraries of polymeric electrophiles.

Example 25

Polymer support variations are also envisioned, including for examplepolymers that can be supported onto beads or other surfaces. One classof polymer support variation that is envisioned is a cast polymer thatcan function as an ion exchange membrane.

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following embodiments. Manyembodiments are described as “comprising” certain components or steps,but alternatively, can “consist essentially of” or “consist of” thosecomponents or steps unless specifically stated otherwise.

Embodiment 1

A process for forming an α,β-unsaturated carboxylic acid or saltthereof, the process comprising

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to        induce a metalalactone elimination reaction to produce the        α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 2

A process for producing an α,β-unsaturated carboxylic acid or a saltthereof, the process comprising:

-   -   (1) contacting        -   (a) a metalalactone comprising at least one ligand;        -   (b) a diluent; and        -   (c) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture comprising an adduct            of the metalalactone and the anionic polyelectrolyte and its            associated metal cations; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 3

A process for producing an α,β-unsaturated carboxylic acid or a saltthereof, the process comprising:

-   -   (1) contacting in any order        -   (a) a transition metal precursor compound comprising at            least one first ligand;        -   (b) optionally, at least one second ligand;        -   (c) an olefin;        -   (d) carbon dioxide (CO₂);        -   (e) a diluent; and        -   (f) an anionic polyelectrolyte having associated metal            cations to provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to form        the α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 4

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte is insoluble in the diluent or the reaction mixture.

Embodiment 5

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte is soluble in the diluent or the reaction mixture.

Embodiment 6

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises an alkoxide, an aryloxide, an acrylate, a(meth)acrylate, a sulfonate, an alkyl thiolate, an aryl thiolate, analkyl amide, or an aryl amine group.

Embodiment 7

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a poly(vinyl aryloxide), a poly(vinylalkoxide), a poly(acrylate), a poly((meth)acrylate), a poly(styrenesulfonate), a phenol-formaldehyde resin, a polyhydroxyarene-formaldehyderesin (such as a resorcinol-formaldehyde resin), a polyhydroxyarene- andfluorophenol-formaldehyde resin (such as a resorcinol- and2-fluorophenol-formaldehyde resin), a poly(vinyl arylamide), apoly(vinyl alkylamide), or combinations thereof.

Embodiment 8

The process according to any one of embodiments 1-5, wherein the anionicpolyelectrolyte comprises any suitable Lewis acidic metal cation or anyLewis acidic metal cation disclosed herein.

Embodiment 9

The process according to any one of embodiments 1-5, wherein theassociated metal cations are an alkali metal, an alkaline earth metal,or a combination thereof.

Embodiment 10

The process according to any one of embodiments 1-5, wherein theassociated metal cations are lithium, sodium, potassium, magnesium,calcium, strontium, barium, aluminum, or zinc.

Embodiment 11

The process according to any one of embodiments 1-5, wherein theassociated metal cations are sodium or potassium.

Embodiment 12

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a poly(vinyl aryloxide), a poly(vinylalkoxide), a substituted analog thereof, or a combination thereof.

Embodiment 13

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises sodium(poly-4-vinylphenoxide).

Embodiment 14

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a phenol-formaldehyde resin, apolyhydroxyarene-formaldehyde resin (such as a resorcinol-formaldehyderesin), a polyhydroxyarene- and fluorophenol-formaldehyde resin (such asa resorcinol- and 2-fluorophenol-formaldehyde resin), or combinationsthereof.

Embodiment 15

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a phenol-formaldehyde resin, aresorcinol-formaldehyde resin, a resorcinol- andfluorophenol-formaldehyde resin, or combinations thereof.

Embodiment 16

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a phenol-formaldehyde resin or a resorcinol-and 2-fluorophenol-formaldehyde resin.

Embodiment 17

The process according to any one of embodiments 1-3, wherein the anionicpolyelectrolyte comprises a phenol-formaldehyde resin.

Embodiment 18

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable non-protic solvent, or any non-proticsolvent disclosed herein.

Embodiment 19

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable weakly coordinating or non-coordinatingsolvent, or any weakly coordinating or non-coordinating solventdisclosed herein.

Embodiment 20

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable aromatic hydrocarbon solvent, or anyaromatic hydrocarbon solvent disclosed herein, e.g., benzene, xylene,toluene, etc.

Embodiment 21

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable ether solvent, or any ether solventdisclosed herein, e.g., THF, dimethyl ether, diethyl ether, dibutylether, etc.

Embodiment 22

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable carbonyl-containing solvent, or anycarbonyl-containing solvent disclosed herein, e.g., ketones, esters,amides, etc. (e.g., acetone, ethyl acetate, N,N-dimethylformamide,etc.).

Embodiment 23

The process according to any one of embodiments 1-17, wherein thediluent comprises any suitable halogenated aromatic hydrocarbon solvent,or any halogenated aromatic hydrocarbon solvent disclosed herein, e.g.,chlorobenzene, dichlorobenzene, etc.

Embodiment 24

The process according to any one of embodiments 1-17, wherein thediluent comprises THF, 2,5-Me₂THF, methanol, acetone, toluene,chlorobenzene, pyridine, or a combination thereof.

Embodiment 25

The process according to any one of the preceding embodiments, whereinthe diluent comprises carbon dioxide.

Embodiment 26

The process according to any one of the preceding embodiments, whereinat least a portion of the diluent comprises the α,β-unsaturatedcarboxylic acid or the salt thereof, formed in the process.

Embodiment 27

The process according to any one of embodiments 3-26, wherein thecontacting step further comprises contacting an additive selected froman acid, a base, or a reductant.

Embodiment 28

The process according to any one of embodiments 3-26, wherein thecontacting step comprises contacting the transition metal precursorcompound comprising at least one first ligand with the at least onesecond ligand.

Embodiment 29

The process according to any one of embodiments 3-26, wherein thecontacting step comprises contacting (a) the transition metal precursorcompound comprising at least one first ligand with (b) the at least onesecond ligand to form a pre-contacted mixture, followed by contactingthe pre-contacted mixture with the remaining components (c)-(f) in anyorder to provide the reaction mixture.

Embodiment 30

The process according to any one of embodiments 1-2 and 4-26, whereinthe contacting step comprises contacting the metalalactone, the diluent,and the anionic polyelectrolyte in any order.

Embodiment 31

The process according to any one of embodiments 1-2 and 4-26, whereinthe contacting step comprises contacting the metalalactone and thediluent to form a first mixture, followed by contacting the firstmixture with the anionic polyelectrolyte to form the reaction mixture.

Embodiment 32

The process according to any one of embodiments 1-2 and 4-26, whereinthe contacting step comprises contacting the diluent and the anionicpolyelectrolyte to form a first mixture, followed by contacting thefirst mixture with the metalalactone to form the reaction mixture.

Embodiment 33

The process according to any one of embodiments 1-26, wherein theconditions suitable to form the α,β-unsaturated carboxylic acid or asalt thereof comprise contacting the reaction mixture with any suitableacid, or any acid disclosed herein, e.g., HCl, acetic acid, etc.

Embodiment 34

The process according to any one of embodiments 1-26, wherein theconditions suitable to form the α,β-unsaturated carboxylic acid or asalt thereof comprise contacting the reaction mixture with any suitablesolvent, or any solvent disclosed herein, e.g., carbonyl-containingsolvents such as ketones, esters, amides, etc. (e.g., acetone, ethylacetate, N,N-dimethylformamide), alcohols, water, etc.

Embodiment 35

The process according to any one of the preceding embodiments, whereinthe conditions suitable to form the α,β-unsaturated carboxylic acid or asalt thereof comprise heating the reaction mixture to any suitabletemperature, or a temperature in any range disclosed herein, e.g., from50 to 1000° C., from 100 to 800° C., from 150 to 600° C., from 250 to550° C., etc.

Embodiment 36

The process according to any one of the preceding embodiments, whereinthe molar yield of the α,β-unsaturated carboxylic acid, or the saltthereof, based on the metalalactone (in those preceding embodimentscomprising a metalalactone) or based on the transition metal precursorcompound (in those preceding embodiments comprising a transition metalprecursor compound) is in any range disclosed herein, e.g., at least20%, at least 40%, at least 60%, at least 80%, at least 100%, at least120%, at least 140%, at least 160%, at least 180%, at least 200%, atleast 250%, at least 300%, at least 350%, at least 400%, at least 450%,or at least 500%, etc.

Embodiment 37

The process according to any one of the preceding embodiments, whereinthe contacting step and/or the forming step is/are conducted at anysuitable pressure or at any pressure disclosed herein, e.g., from 5 psig(34 KPa) to 10,000 psig (68,948 KPa), from 45 psig (310 KPa) to 1000psig (6,895 KPa), etc.

Embodiment 38

The process according to any one of the preceding embodiments, whereinthe contacting step and/or the applying step is/are conducted at anysuitable temperature or at any temperature disclosed herein, e.g., from0° C. to 250° C., from 0° C. to 95° C., from 15° C. to 70° C., etc.

Embodiment 39

The process according to any one of the preceding embodiments, whereinthe contacting step is conducted at any suitable weight hourly spacevelocity (WHSV) or any WHSV disclosed herein, e.g., from 0.05 to 50hr⁻¹, from 1 to 25 hr⁻¹, from 1 to 5 hr⁻¹, etc., based on the amount ofthe anionic polyelectrolyte.

Embodiment 40

The process according to any one of the preceding embodiments, whereinthe process further comprises a step of isolating the α,β-unsaturatedcarboxylic acid, or the salt thereof, e.g., using any suitableseparation/purification procedure or any separation/purificationprocedure disclosed herein, e.g., evaporation, distillation,chromatography, etc.

Embodiment 41

The process according to any one of embodiments 1-40, wherein theanionic polyelectrolyte of the contacting step (1) comprises a fixedbed.

Embodiment 42

The process according to any one of embodiments 1-40, wherein theanionic polyelectrolyte of the contacting step (1) is supported ontobeads or is used in the absence of a support.

Embodiment 43

The process according to any one of embodiments 1-40, wherein thecontacting step (1) is carried out by mixing/stirring the anionicpolyelectrolyte in the diluent.

Embodiment 44

The process according to any one of the preceding embodiments, whereinthe α,β-unsaturated carboxylic acid or a salt thereof comprises anysuitable α,β-unsaturated carboxylic acid, or any α,β-unsaturatedcarboxylic acid disclosed herein, or a salt thereof, e.g., acrylic acid,methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodium acrylate,potassium acrylate, magnesium acrylate, sodium (meth)acrylate, etc.

Embodiment 45

The process according to any one of embodiments 1-2 or 4-44, furthercomprising a step of contacting a transition metal precursor compoundcomprising at least one first ligand, an olefin, and carbon dioxide(CO₂) to form the metalalactone comprising at least one ligand.

Embodiment 46

The process according to any one of embodiments 1-2 or 4-44, furthercomprising a step of contacting a transition metal precursor compoundcomprising at least one first ligand, at least one second ligand, anolefin, and carbon dioxide (CO₂) to form the metalalactone comprising atleast one ligand.

Embodiment 47

The process according to embodiment 46, wherein the metalalactone ligandcomprises the at least one first ligand, the at least one second ligand,or a combination thereof.

Embodiment 48

The process according to embodiment 46, wherein the metalalactone ligandcomprises the at least one second ligand.

Embodiment 49

The process according to any one of embodiments 3 or 45, wherein theolefin comprises any suitable olefin or any olefin disclosed herein,e.g. ethylene, propylene, butene (e.g., 1-butene), pentene, hexene(e.g., 1-hexene), heptane, octene (e.g., 1-octene), styrene, etc.

Embodiment 50

The process according to any one of embodiments 3 or 45-49, wherein theolefin is ethylene, and the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) is conductedusing any suitable pressure of ethylene, or any pressure of ethylenedisclosed herein, e.g., from 10 psig (69 KPa) to 1,000 psig (6895 KPa),from 25 psig (172 KPa) to 500 psig (3,447 KPa), or from 50 psig (345KPa) to 300 psig (2,068 KPa), etc.

Embodiment 51

The process according to any one of embodiments 3 or 45-49, wherein theolefin is ethylene, and the step of contacting a transition metalprecursor compound with an olefin and carbon dioxide (CO₂) is conductedusing a constant addition of the olefin and carbon dioxide to providethe reaction mixture.

Embodiment 52

The process according to embodiment 51, wherein the ethylene and carbondioxide (CO₂) are constantly added in an ethylene:CO₂ molar ratio offrom 3:1 to 1:3, to provide the reaction mixture.

Embodiment 53

The process according to any one of embodiments 3 or 45-49, wherein thestep of contacting a transition metal precursor compound with the olefinand carbon dioxide (CO₂) is conducted using any suitable pressure ofCO₂, or any pressure of CO₂ disclosed herein, e.g., from 20 psig (138KPa) to 2,000 psig (13,790 KPa), from 50 psig (345 KPa) to 750 psig(5,171 KPa), or from 100 psig (689 KPa) to 300 psig (2,068 KPa), etc.

Embodiment 54

The process according to any one of the preceding embodiments, furthercomprising a step of monitoring the concentration of at least onereaction mixture component, at least one elimination reaction product,or a combination thereof.

Embodiment 55

The process according to any one of embodiments 1-54, wherein the metalof the metalalactone or the metal of the transition metal precursorcompound is a Group 8-11 transition metal.

Embodiment 56

The process according to any one of embodiments 1-54, wherein the metalof the metalalactone or the metal of the transition metal precursorcompound is Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, or Au.

Embodiment 57

The process according to any one of embodiments 1-54, wherein the metalof the metalalactone or the metal of the transition metal precursorcompound is Ni, Fe, or Rh.

Embodiment 58

The process according to any one of embodiments 1-54, wherein the metalof the metalalactone or the metal of the transition metal precursorcompound is Ni.

Embodiment 59

The process according to any one of embodiments 1-2 or 4-44, wherein themetalalactone is a nickelalactone, e.g., any suitable nickelalactone orany nickelalactone disclosed herein.

Embodiment 60

The process according to any one of embodiments 1-54, wherein any of themetalalactone ligand, the first ligand, or the second ligand is anysuitable neutral electron donor group and/or Lewis base, or any neutralelectron donor group and/or Lewis base disclosed herein.

Embodiment 61

The process according to any one of embodiments 1-54, wherein any of themetalalactone ligand, the first ligand, or the second ligand is abidentate ligand.

Embodiment 62

The process according to any one of embodiments 1-54, wherein any of themetalalactone ligand, the first ligand, or the second ligand comprisesat least one of a nitrogen, phosphorus, sulfur, or oxygen heteroatom.

Embodiment 63

The process according to any one of embodiments 1-54, wherein any of themetalalactone ligand, the first ligand, or the second ligand comprisesor is selected from a diphosphine ligand, a diamine ligand, a dieneligand, a diether ligand, or dithioether ligand.

Embodiment 64

The process according to any one of embodiments 1-63, further comprisingthe step of regenerating the anionic polyelectrolyte by contacting theanionic polyelectrolyte with a base comprising a metal cation followingthe formation of the α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 65

The process according to embodiment 64, further comprising a step ofwashing the anionic polyelectrolyte with a solvent or the diluent.

Embodiment 66

The process according to embodiment 64, wherein the base comprises ametal cation is any suitable base, or any base disclosed herein, e.g.,carbonates (e.g., Na₂CO₃, Cs₂CO₃, MgCO₃), hydroxides (e.g., Mg(OH)₂,NaOH), alkoxides (e.g., Al(O^(i)Pr)₃, Na(O^(t)Bu), Mg(OEt)₂), and thelike.

Embodiment 67

The process according to embodiment 64, wherein the step of regeneratingthe anionic polyelectrolyte is carried out in the absence of analkoxide, an aryloxide, an amide, an alkylamide, an arylamide, an amine,a hydride, a phosphazene, and/or substituted analogs thereof.

Embodiment 68

The process according to embodiment 64, wherein the step of regeneratingthe anionic polyelectrolyte is carried out in the absence of analkoxide, an aryloxide, a hydride, and/or a phosphazene.

Embodiment 69

The process according to embodiment 64, wherein the step of regeneratingthe anionic polyelectrolyte is carried out in the absence of anaryloxide or a metal hydride.

Embodiment 70

The process according to embodiment 64, wherein the step of regeneratingthe anionic polyelectrolyte is carried out in the absence of anon-nucleophilic base.

Embodiment 71

The process according to embodiment 64, wherein the anionicpolyelectrolyte is unsupported.

Embodiment 72

The process according to any one of embodiments 1-3, wherein themetalalactone, metalalactone ligand, transition metal precursorcompound, first ligand, second ligand, anionic polyelectrolyte, or metalcation is any suitable metalalactone, metalalactone ligand, transitionmetal precursor compound, first ligand, second ligand, anionicpolyelectrolyte, or metal cation or is any metalalactone, metalalactoneligand, transition metal precursor compound, first ligand, secondligand, anionic polyelectrolyte, or metal cation disclosed herein.

Embodiment 73

A process for forming an α,β-unsaturated carboxylic acid or saltthereof, the process comprising:

-   -   (1) contacting        -   (a) a metalalactone comprising a Group 8-10 metal and at            least one ligand;        -   (b) a diluent; and        -   (c) a polyaromatic resin with associated metal cations to            provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to        induce a metalalactone elimination reaction to form the        α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 74

A for producing an α,β-unsaturated carboxylic acid or a salt thereof,the process comprising:

-   -   (1) contacting in any order        -   (a) a group 8-11 transition metal precursor;        -   (b) an olefin;        -   (c) carbon dioxide (CO₂);        -   (d) a diluent; and        -   (e) a polyaromatic resin with associated metal cations to            provide a reaction mixture; and    -   (2) applying conditions to the reaction mixture suitable to        produce the α,β-unsaturated carboxylic acid or a salt thereof.

Embodiment 75

A process for producing an α,β-unsaturated carboxylic acid or a saltthereof, the process comprising:

-   -   (1) contacting in any order        -   (a) a group 8-11 transition metal catalyst;        -   (b) an olefin;        -   (c) carbon dioxide (CO₂);        -   (d) a diluent; and        -   (e) an anionic polyelectrolyte with associated metal cations            to provide a reaction mixture; and    -   (2) contacting the reaction mixture with a metal-containing base        selected from an alkali metal or an alkaline earth metal oxide,        hydroxide, alkoxide, aryloxide, amide, alkyl amide, arylamide,        or carbonate to produce an α,β-unsaturated carboxylic acid salt;        -   wherein the contacting step is carried out in the absence of            a non-nucleophilic base.

We claim:
 1. A process for forming an α,β-unsaturated carboxylic acid orsalt thereof, the process comprising (1) contacting (a) a metalalactonecompound comprising a Group 8-10 metal; (b) a diluent; and (c) ananionic polyaromatic resin with associated metal cations to provide areaction mixture; (2) applying conditions to the reaction mixturesuitable to induce a metalalactone elimination reaction to form theα,β-unsaturated carboxylic acid or a salt thereof and a polyaromaticresin; and (3) regenerating the anionic polyaromatic resin by contactingthe polyaromatic resin with a base comprising a metal cation followingthe formation of the α,β-unsaturated carboxylic acid or the saltthereof.
 2. The process according to claim 1, wherein the anionicpolyaromatic resin with associated metal cations comprises a metallatedphenol-formaldehyde resin, a metallated polyhydroxyarene-formaldehyderesin, or a metallated polyhydroxyarene- and fluorophenol-formaldehyderesin.
 3. The process according to claim 1, wherein the anionicpolyaromatic resin with associated metal cations comprises a sodiumphenol-formaldehyde resin, a potassium phenol-formaldehyde resin, asodium resorcinol- and 2-fluorophenol-formaldehyde resin, or a potassiumresorcinol- and 2-fluorophenol-formaldehyde resin.
 4. The processaccording to claim 1, wherein the anionic polyaromatic resin withassociated metal cations is insoluble in the diluent or the reactionmixture.
 5. The process according to claim 1, wherein the reactionmixture comprises an adduct of the metalalactone compound and theanionic polyaromatic resin with associated metal cations.
 6. The processaccording to claim 1, wherein the contacting step comprises contactingthe metalalactone compound, the diluent, and the anionic polyaromaticresin with associated metal cations in any order.
 7. The processaccording to claim 1, wherein the conditions suitable to induce ametalalactone elimination reaction comprise contacting the reactionmixture with a metal-containing base selected from an alkali metal or analkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkylamide, arylamide, or carbonate, and wherein the contacting step iscarried out in the absence of sodium hydride.
 8. The process accordingto claim 1, wherein the metalalactone compound comprises Ni.
 9. Aprocess for producing an α,β-unsaturated carboxylic acid or a saltthereof, the process comprising: (1) contacting in any order (a) a group8-11 transition metal precursor; (b) an olefin; (c) carbon dioxide(CO₂); (d) a diluent; and (e) an anionic polyaromatic resin withassociated metal cations to provide a reaction mixture; and (2) applyingconditions to the reaction mixture suitable to produce theα,β-unsaturated carboxylic acid or a salt thereof; and (3) regeneratingthe anionic polyaromatic resin by contacting the polyaromatic resin witha base comprising a metal cation following the formation of theα,β-unsaturated carboxylic acid or the salt thereof.
 10. The processaccording to claim 9, wherein the reaction mixture comprises an adductof a metalalactone compound and the anionic polyaromatic resin withassociated metal cations.
 11. The process according to claim 9, whereinthe anionic polyaromatic resin with associated metal cations comprises ametallated phenol-formaldehyde resin, a metallatedpolyhydroxyarene-formaldehyde resin, or a metallated polyhydroxyarene-and fluorophenol-formaldehyde resin.
 12. The process according to claim9, wherein the anionic polyaromatic resin with associated metal cationscomprises a sodium phenol-formaldehyde resin, a potassiumphenol-formaldehyde resin, a sodium resorcinol- and2-fluorophenol-formaldehyde resin, or a potassium resorcinol- and2-fluorophenol-formaldehyde resin.
 13. The process according to claim 9,wherein the conditions suitable to produce the α,β-unsaturatedcarboxylic acid or a salt thereof comprise contacting the reactionmixture with a metal-containing base selected from an alkali metal or analkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkylamide, arylamide, or carbonate, and wherein the contacting step iscarried out in the absence of sodium hydride.
 14. The process accordingto claim 9, wherein the olefin comprises ethylene, propylene, butene,pentene, hexene, heptene, octene, or styrene.
 15. The process accordingto claim 9, wherein the olefin is ethylene, and the step of contactingthe group 8-11 transition metal precursor with the olefin and carbondioxide is conducted using from 10 psig (689 KPa) to 1,000 psig (6,902KPa) of ethylene partial pressure.
 16. The process according to claim 9,wherein the olefin is ethylene, and the step of contacting the group8-11 transition metal precursor with the olefin and carbon dioxide isconducted using a constant addition of the olefin and carbon dioxide andthe ethylene and carbon dioxide are added in a constant or a variableethylene:CO₂ molar ratio of from 10:1 to 1:10, to provide the reactionmixture.
 17. The process according to claim 9, wherein the group 8-11transition metal precursor comprises Ni.
 18. The process according toclaim 9, wherein the diluent comprises a non-protic solvent, a weaklycoordinating solvent, or a non-coordinating solvent.
 19. The processaccording to claim 9, wherein the diluent comprises an aromatichydrocarbon solvent, an ether solvent, a carbonyl-containing solvent, ahalogenated aromatic hydrocarbon solvent, or combinations thereof. 20.The process according to claim 9, wherein a molar yield of theα,β-unsaturated carboxylic acid, or the salt thereof based on thetransition metal precursor compound is at least 100%.
 21. The processaccording to claim 9, wherein the conditions suitable to produce theα,β-unsaturated carboxylic acid or a salt thereof comprise at least oneof the following conditions or any combination of the followingconditions: a) contacting the reaction mixture with a ketone, an ester,an amide, an alcohol, or water; b) heating the reaction mixture to atemperature from 50 to 1000° C.; c) conducting the contacting step at atotal pressure of from 5 psig (34 KPa) to 10,000 psig (68,948 KPa); d)conducting the contacting step at a temperature of from 0° C. to 250°C.; and/or e) conducting the contacting step at a weight hourly spacevelocity (WHSV) of from 0.05 to 50 hr⁻¹, based on the amount of theanionic polyaromatic resin with associated metal cations.
 22. A processfor producing an α,β-unsaturated carboxylic acid or a salt thereof, theprocess comprising: (1) contacting in any order (a) a group 8-11transition metal catalyst; (b) an olefin; (c) carbon dioxide (CO₂); (d)a diluent; and (e) an anionic polyelectrolyte with associated metalcations to provide a reaction mixture; and (2) contacting the reactionmixture with a metal-containing base selected from an alkali metal or analkaline earth metal oxide, hydroxide, alkoxide, aryloxide, amide, alkylamide, arylamide, or carbonate to produce an α,β-unsaturated carboxylicacid salt; wherein the contacting step is carried out in the absence ofsodium hydride; and (3) regenerating the anionic polyaromatic resin bycontacting the polyaromatic resin with a base comprising a metal cationfollowing the formation of the α,β-unsaturated carboxylic acid or thesalt thereof.
 23. The process according to claim 22, further comprisingthe step of acidifying the α,β-unsaturated carboxylic acid salt to forman α,β-unsaturated carboxylic acid.
 24. The process according to claim22, wherein: the group 8-11 transition metal catalyst comprises nickel;the olefin comprises ethylene; and the anionic polyaromatic resin isselected from a metallated poly(vinyl aryloxide), poly(vinyl alkoxide),phenol-formaldehyde resin, polyhydroxyarene-formaldehyde resin, orpolyhydroxyarene- and fluorophenol-formaldehyde resin, each with theirrespective associated metal cations.
 25. The process according to claim24, wherein the anionic polyaromatic resin with associated metal cationsis selected from a sodium phenol-formaldehyde resin, a potassiumphenol-formaldehyde resin, a sodium resorcinol- and2-fluorophenol-formaldehyde resin, or a potassium resorcinol- and2-fluorophenol-formaldehyde resin.
 26. The process according to claim 1,further comprising a step of washing the regenerated anionicpolyaromatic resin with a solvent or the diluent.
 27. The processaccording to claim 1, wherein the base comprises a carbonate, ahydroxide, or an alkoxide.
 28. The process according to claim 1, whereinthe base comprises Na₂CO₃, Cs₂CO₃, MgCO₃, Mg(OH)₂, NaOH, KOH,Al(O^(i)Pr)₃, Na(O^(t)Bu), or Mg(OEt)₂.
 29. The process according toclaim 1, wherein the step of regenerating the anionic polyaromatic resinis carried out in the absence of an alkoxide, an aryloxide, an amide, analkylamide, an arylamide, an amine, a hydride, or a phosphazene, orsubstituted analogs thereof.
 30. The process according to claim 1,wherein the step of regenerating the anionic polyaromatic resin iscarried out in the absence of an aryloxide or a metal hydride.
 31. Theprocess according to claim 1, wherein the step of regenerating theanionic polyaromatic resin is carried out in the absence of sodiumhydride.
 32. The process according to claim 1, wherein the anionicpolyaromatic resin is unsupported.
 33. The process according to claim 9,wherein the base comprises a carbonate, a hydroxide, or an alkoxide. 34.The process according to claim 9, wherein the base comprises Na₂CO₃,Cs₂CO₃, MgCO₃, Mg(OH)₂, NaOH, KOH, Al(O^(i)Pr)₃, Na(O^(t)Bu), orMg(OEt)₂.
 35. The process according to claim 9, wherein the step ofregenerating the anionic polyaromatic resin is carried out in theabsence of an alkoxide, an aryloxide, an amide, an alkylamide, anarylamide, an amine, a hydride, or a phosphazene, or substituted analogsthereof.
 36. The process according to claim 9, wherein the step ofregenerating the anionic polyaromatic resin is carried out in theabsence of an aryloxide or a metal hydride.
 37. The process according toclaim 22, wherein the base comprises a carbonate, a hydroxide, or analkoxide.
 38. The process according to claim 22, wherein the basecomprises Na₂CO₃, Cs₂CO₃, MgCO₃, Mg(OH)₂, NaOH, KOH, Al(O^(i)Pr)₃,Na(O^(t)Bu), or Mg(OEt)₂.
 39. The process according to claim 22, whereinthe step of regenerating the anionic polyaromatic resin is carried outin the absence of an alkoxide, an aryloxide, an amide, an alkylamide, anarylamide, an amine, a hydride, or a phosphazene, or substituted analogsthereof.
 40. The process according to claim 22, wherein the step ofregenerating the anionic polyaromatic resin is carried out in theabsence of an aryloxide or a metal hydride.